Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
  • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
  • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
  • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

• the present invention relates to certain new triazolylbenzyloxy-ketones and -carbinols, to several processes for their production and to their use as fungicides.
• 3,3-dimethyl-1-phenoxy-1-triazolyl-butan-2-ones and -ols which are substituted in the phenyl part such as 3,3-dimethyl-1-(4-tert.-butylphenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one or -ol and 3,3-dimethyl-1-(penta-chlorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one, in general have good fungicidal properties (see U.S. Pat. Nos. 3,912,752 and 3,952,002). However, their action is not always completely satisfactory in some fields of application, especially when low amounts and concentrations are applied.
• the present invention now provides, as new compounds, the triazolyl-benzyloxy-ketones and -carbinols of the general formula ##STR2## in which A represents a keto group or a CH(OH) grouping,
• X represents a halogen atom or an alkyl or halogenoalkyl radical
• n 0, 1, 2, 3, 4 or 5
• the new triazolyl-benzyloxy-ketones and -carbinols of the present invention have powerful fungicidal properties.
• the componds according to the invention exhibit a better fungicidal activity than the compounds 3,3-dimethyl-1-(4-tert.-butyl-phenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one or -ol and 3,3-dimethyl-1-(pentachlorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one, which are known from the state of the art and are closely related compounds chemically and from the point of view of their action.
• the substances according to the invention thus represent an enrichment of the art.
• Preferred triazolyl-benzyloxy-ketones and -carbinols according to the present invention are those of formula (I) in which X represents a halogen atom, a straight-chain or branched alkyl radical with 1 to 4 carbon atoms or a halogenoalkyl radical with 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as, preferably fluorine or chlorine atoms, n is 0, 1, 2 or 3 and A has the above-mentioned meaning.
• Very particularly preferred compounds of the formula (I) are those in which X represents a fluorine, chlorine or bromine atom or a methyl or trifluoromethyl radical, n is 0, 1 or 2, and A has the above-mentioned meaning.
• Hal represents a chlorine or bromine atom
• an acid or a metal salt can then be added onto the compounds of the present invention thus obtained.
• halogenoether-ketones to be used as starting compounds of formula (II) for process variant (a) are those in which X and n have meanings which have already been mentioned as preferred in connection with the description of the preferred and particularly preferred compounds of the present invention.
• halogenoether-ketones of the formula (II) are novel; however, they can be prepared by known processes, for example by a procedure in which in benzyl ethers of the general formula ##STR10## in which X and n have the above-mentioned meaning, one of the two active hydrogen atoms is replaced by chlorine and bromine in the customary manner.
• the halogenoether-ketones of the formula (II) formed can be further reacted directly, without being isolated (see also the Preparative Examples).
• the benzyl ethers of the formula (V) can be obtained by known processes, for example by a procedure in which benzyl alcohols of the formula (IV) are reacted with chloro(bromo)-pinacolin of the formula
• phase transfer catalyst such as ammonium compounds, for example triethylbenzyl-ammonium chloride.
• Triazolylhalogeno-ketones to be used as starting compounds of formula (III) for process variant (b) are known (see U.S. application Ser. No. 964,768, filed Nov. 29, 1978). They are obtained by a procedure in which chloro(bromo)-pinacolin of the formula (VI) is reacted with 1,2,4-triazole in the presence of an acid-binding agent, such as potassium carbonate, and in the presence of an inert organic solvent, such as acetone, at temperatures between 60° and 120° C. One of the two active hydrogen atoms is then replaced by chlorine or bromine in the customary manner.
• an acid-binding agent such as potassium carbonate
• an inert organic solvent such as acetone
• Particularly preferred benzyl alcohols also to be used as starting componds of formula (IV) for process variant (b) are those in which X and n have meanings which have already been mentioned in connection with the description of the preferred and particularly preferred compounds of the present invention.
• the benzyl alcohols of the formula (V) are generally known compounds of organic chemistry.
• Possible diluents for the reaction, according to the invention, in process variants (a) and (b) are inert organic solvents. These include, preferably, ketones such as diethyl ketone, and in particular acetone and methyl ethyl ketone, nitriles, such as propionitrile, and in particular acetonitrile; alcohols, such as ethanol or isopropanol; ethers, such as tetrahydrofuran or dioxane; benzene; formamides; such as, in particular, dimethyl formamide; and halogenated hydrocarbons.
• ketones such as diethyl ketone, and in particular acetone and methyl ethyl ketone
• nitriles such as propionitrile, and in particular acetonitrile
• alcohols such as ethanol or isopropanol
• ethers such as tetrahydrofuran or dioxane
• the reactions in process variants (a) and (b) are carried out in the presence of an acid-binding agent.
• an acid-binding agent such as alkali metal carbonates (for example sodium carbonate, potassium carbonate and sodium bicarbonate), silver carbonate, C 1 to C 4 tertiary alkylamines, cycloalkylamines, or aralkylamines (for example triethylamine or dimethylbenzylamine) pyridine and diazabicyclooctane.
• the reaction temperature can be varied within a substantial range in process variants (a) and (b).
• the reactions are carried out between 20° and 150° C., preferably at 60° to 120° C. If a solvent is present, it is expedient to carry out the reaction at the boiling point of the particular solvent.
• 1 to 2 moles of 1,2,4-triazole or 1 to 2 moles of benzyl alcohol of the formula (IV) and in each case 1 to 2 moles of acid binding agent are preferably employed per mole of the compound of the formula (II) or (III).
• the solvent is distilled off and either water is added to the residue and the mixture is stirred vigorously, whereupon the reaction product crystallizes completely, or the residue is taken up in a mixture of an organic solvent and water and the organic phase is separated off, washed with water, dried over sodium sulphate and freed from the solvent in vacuo. If appropriate, the residue is purified by distillation or recrystallization.
• process variant (c) is carried out in the customary manner, for example by reaction with complex hydrides, if appropriate in the presence of a diluent, or by reaction with aluminum isopropylate in the presence of a diluent.
• polar organic solvents include, preferably, alcohols, such as methanol, ethanol, butanol and isopropanol, and ethers, such as diethyl ether or tetrahydrofuran.
• the reaction is in general carried out at 0° to 30° C., preferably at 0° to 20° C.
• a complex hydride such as sodium borohydride or lithium alanate
• the residue is taken up in dilute hydrochloric acid and the mixture is then rendered alkaline and extracted with an organic solvent. Further working up is carried out in the customary manner.
• reaction temperatures can again be varied within a substantial range; in general, the reaction is carried out between 20° and 120° C., preferably 50° to 100° C.
• about 1 to 2 moles of aluminum isopropylate are employed per mole of the ketone of the formula (Ia).
• the excess solvent is removed by distillation in vacuo, and dilute sulphuric acid or sodium hydroxide solution is added to the aluminum compound formed. Further working up is carried out in the customary manner.
• the following acids can preferably be used for the preparation of physiologically acceptable acid addition salts of the compounds of the formula (I): hydrogen halide acids (such as hydrobromic acid, and, in particular, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid), and sulphonic acids (such as p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid).
• hydrogen halide acids such as hydrobromic acid, and, in particular, hydrochloric acid
• phosphoric acid such as hydrobromic acid, and, in particular, hydrochloric acid
• phosphoric acid such as hydrobromic acid, and, in particular, hydrochloric acid
• phosphoric acid such as hydrobromic acid, and, in particular,
• the acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid for example hydrochloric acid, and they can be isolated in a known manner, for example by filtration, and if appropriate purified by washing with an inert organic solvent.
• Salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII are preferably used for the preparation of metal salt complexes of the compounds of the formula (I), examples of metals which may be mentioned being copper, zinc, manganese, magnesium, tin, iron and nickel.
• Possible anions of the salts are preferably those which are derived from the following acids: hydrogen halide acids, such as hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid, nitric acid and sulphuric acid.
• the metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I).
• the metal salt complexes can be purified in a known manner, for example by filtration, isolation and, if appropriate by recrystallization.
• the active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired microorganisms.
• the active compounds are suitable for use as plant protection agents.
• Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidomycetes, and Deuteromycetes.
• the good toleration, by plants, of the active compounds at the concentrations required for combating plant diseases permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
• the active compounds according to the invention can be used with particularly good success for combating cereal diseases, such as powdery mildew of cereal and powdery mildew of barley; and Venturia species, such as against the apple scab causative organism (Fusicladium dendriticum); and for combating powdery mildew of cucumber (Erysiphe cichoriacearum).
• cereal diseases such as powdery mildew of cereal and powdery mildew of barley
• Venturia species such as against the apple scab causative organism (Fusicladium dendriticum); and for combating powdery mildew of cucumber (Erysiphe cichoriacearum).
• the active compounds according to the invention not only have a protective action but also have a systemic action. Thus, it is possible to protect plants from fungal attack if the active compound is fed to the above-ground parts of the plant via the soil and the root or via the seed.
• the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
• formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents.
• extenders that is to say liquid or liquefied gaseous or solid diluents or carriers
• surface-active agents that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents.
• organic solvents can, for example, also be used as auxiliary solvents.
• liquid diluents or carriers especially solvents
• aromatic hydrocarbons such as xylene, toluene or alkyl naphthalenes
• chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
• aliphatic or alicyclic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions
• alcohols such as butanol or glycol as well as their ethers and esters
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
• strongly polar solvents such as dimethylformamide and dimethylsulphoxide, as well as water.
• liquefied gaseous diluents or carriers liquids which would be gaseous at normal temperatures and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
• ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillontice or diatomaceous earth
• ground synthetic minerals such as highly-dispersed silicic acid, alumina and silicates.
• crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.
• non-ionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulpates, aryl sulphonates as well as albumin hydrolysis products.
• Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
• Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules of latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
• colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
• organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs
• trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
• the formulations in general contain from 0.1 to 95 percent by weight of active compound, preferably from 0.5 to 90 percent by weight.
• the active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and agents for improving soil structure.
• active compounds such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients and agents for improving soil structure.
• the active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions powders, pastes and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomizing, misting, vaporizing, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
• the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.
• active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% are generally required at the place of action.
• the compounds according to the invention When applied in appropriate amounts, the compounds according to the invention also exhibit a growth-regulating action.
• the present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
• the present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
• the present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
• active compound 0.25 part by weight of active compound was taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier (alkylaryl polyglycol ether), and 975 parts by weight of water were added. The concentrate was diluted with water to the desired final concentration of the spray liquor.
• emulsifier alkylaryl polyglycol ether
• the degree of infection was expressed as a percentage of the infection of the untreated control plants. 0% denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control. The more active the compound, the lower was the degree of mildew infection.
• Powdery mildew of barley test (Erysiphe graminis var. hordei)/systemic (fungal disease of cereal shoots)
• the active compounds were used as pulverulent seed treatment agents. These were produced by extending the active compound with a mixture of equal parts by weight of talc and kieselguhr to give a finely pulverulent mixture of the desired concentration of active compound.
• barley seed was shaken with the extended active compound in a closed glass bottle.
• the seed was sown at the rate of 3 ⁇ 12 grains in flowerpots, 2 cm deep in a mixture of one part by volume of Fruhstorfer standard soil and one part by volume of quartz sand.
• the germination and emergence took place under favorable conditions in a greenhouse. 7 days after sowing, when the barley plants had unfolded their first leaf, they were dusted with fresh spores of Erysiphe graminis var. hordei and grown on at 21°-22° C. and 80-90% relative atmospheric humidity and 16 hours' exposure to light.
• the typical mildew pustules formed on the leaves within 6 days.
• the degree of infection was expressed as a percentage of the infection of the untreated control plants. Thus, 0% denoted no infection and 100% denoted the same degree of infection as in the case of the untreated control. The more active the compound, the lower was the degree of mildew infection.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
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• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Plural Heterocyclic Compounds (AREA)

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Citations (4)

• 1980
  • 1980-04-02 DE DE19803012824 patent/DE3012824A1/de not_active Withdrawn
• 1981
  • 1981-03-19 US US06/245,288 patent/US4380545A/en not_active Expired - Fee Related
  • 1981-03-20 EP EP81102090A patent/EP0039405A3/fr not_active Withdrawn
  • 1981-03-20 DD DD81228485A patent/DD157533A5/de unknown
  • 1981-03-23 PT PT72714A patent/PT72714B/pt unknown
  • 1981-03-30 PL PL23043181A patent/PL230431A1/xx unknown
  • 1981-03-30 AU AU68886/81A patent/AU6888681A/en not_active Abandoned
  • 1981-03-30 JP JP4569581A patent/JPS56156269A/ja active Pending
  • 1981-03-31 IL IL62536A patent/IL62536A0/xx unknown
  • 1981-03-31 ES ES500891A patent/ES500891A0/es active Granted
  • 1981-04-01 BR BR8101983A patent/BR8101983A/pt unknown
  • 1981-04-01 ZA ZA00812169A patent/ZA812169B/xx unknown
  • 1981-04-01 DK DK148381A patent/DK148381A/da not_active Application Discontinuation

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